Polyazo dyestuffs



United States Patent Q POLYAZO DYESTUFFS Hans-Rudolf Byland, Riehen, near Basel, Switzerland, assignor, by mesne assignments, to Saul & C0., Newark, N. J., as nominee of Fidelity Union Trust Company, executive trustee under Sandoz Trust No Drawing. Application March 14, 1955 Serial No. 494,295

Claims priority, application Switzerland October 20, 1952 7 Claims. (Cl. 260-168) X X wherein X stands for OH, 003 1a,, ocH,.co0H

or COOH, Y stands for a moiety corresponding to the formula ()H (I) Z stands for the radical of a coupling component corresponding to the aforesaid Formula I or for the radical of a coupling component of the benzene or naphthalene series, R stands for hydrogen, lower alkyl, cycloalkyl, aralkyl or aryl, and the nucleus A is free from carboxylic acid groups but maybe otherwise substituted or unsubstituted.

More particularly, the invention is concerned with a group of copperable polyazo dyestuffs which correspond to the formula H H038 NH V w to OH 2,842,538 Patented July 8, 1958 2 wherein w stands for OCH or COOH, a stands for hydrogen or NHR, b stands for hydrogen or for the radical of the formula 4 11 is one of the numerals 0 and 1, R stands for hydrogen,

15 lower alkyl, cycloalkyl, aralkyl or aryl, nucleus A is free from carboxylic acid groups but may be otherwise substituted or unsubstituted, and wherein OH in nucleus B is in orthoposition to the adjacent N=N group. The aforesaid dyestuffs are obtained, according to the present invention, by coupling one mol of the tetrazo compound of a 4,4'-diamino-1,1'-diphenyl of the formula wherein X has the precedingly-indicated significance, with two mols of an azo compound of the formula noas- NHR wherein R has the precedingly-indicated significance and nucleus A may be further unsubstituted or may carry ously or in any desired order of succession with one mol of an azo compound (III) as hereinbefore described and substituents other than the carboxyl group, or simultaneone mol of a different azo compound corresponding to the said Formula III, or in any desired order of succession with one mol of an azo compound (III) as initially defined and one mol of any other desired azo compound containing one or more groups capable of meta] complex formation.

4,4'-diarnino-l,l-diphenyls of the Formula II, Which are suitable for preparation of the new polyazo dyestuffs according to the aforesaid processes, comprise 4,4-diamino-3,3-dihydroxy-1,l-diphenyl, 4,4'-diamino-3,3-di methoxy-1,1-diphenyl, 4,4-diamino-3,3'-diethoxy-1,1-diphenyl, 4,4-diamino-3,3-dicarboxymethoxy-l,1-diphenyl and 4,4'-diamino-1,1-diphenyl-3,3'-dicarboxylic acid.

Azo compounds of Formula III can be prepared by coupling diazotized 1-amino-Z-hydroxybenzenes with 2 amino-5-hydroxynaphthalene-7-sulfonic 'acids' and l-l substituted derivatives thereof, in acid medium. Suitable 1-amino-2-hydroxybenzenes comprise for example 1- amino-Z-hydroxybenzene itself, l-arnino-Z-hydro-xybenzene-4-sulfonic acid, 1-amino-2-hydroxybenzene-5-sulfonic acid, 1-amino-2-hydroxybenzene-S-sulfonic acid amide and its derivatives which are methylated, ethylated, dimethylated and diethylated at the sulfonamide nitrogen,

1-amino-2-hydroxybenzeneS-sulfonic acid-phenylamide and derivatives which are halogenated, alkylated or alkoxylated in the nucleus of the phenylamide group as well as otherwise substituted derivatives such as l-amino- Z-hydrox'ybenzene-5-sulfonic acid (3' carboxy 4 hydroxy)-phenylamide, also 1-amino-2-hydroxy-S-chlorobenzene-4-sulfonic acid, 1-amino-2-hydroxy-5-nitrobenzene-4-sulfonic acid, 1-amino-2-hydroxy-3-nitroor -chloroor -bromobenzene-5-sulfonic acid and the isomeric compounds wherein the substituents in the 3- sulfonic acid are alkyl and cycloalkyl radicals such for example as methyl, ethyl, propyl, hydroxyethyl and cyclohexyl, mononuclear aryl radicals such as phenyl, (2- methyl) -phenyl, 3-methyl) -phenyl, (4'-methyl) -phenyl, (3' chloro) phenyl, (4' chloro) phenyl, K-amino)- phenyl, (4' carboxy) phenyl, (3-carboxy-4'-hydroxy)- phenyl, (3-sulfo)-phenyl and (4'-sulfo)-phenyl, and also binuclear aryl radicals such as (4-arnino)-1,l"-diphenyl as well as aralkyl radicals such as benzyl and the like.

The new polyazo dyestuffs may be symmetrical or unsymmetrical in their structure. For the preparation of unsymmetrical products, the tetrazotized 4,4-diamino- 1,1-diphenyl (II) is coupled for example with two different azo compounds corresponding to Formula III.

The unsymmetrical polyazo dyestuffs can, however, also be prepared by coupling one mol of tetrazotized compound (II) with one mol of compound (III) and one mol of any other desired azo compound containing one or more groups capable of metal complex formation. Particularly well suited azo components for this purpose are for example 1-hydroxybenzene-Z-carboxylic acid, l-hydroxy-6-methylbenzene 2 carboxylic acid, 1 hydroxynaphthalene-Z-carboxylic acid, 2-hydroxynaphthalene-3- carboxylic acid, 1-hydroxynaphtlialenel-sulfonic acid, 1-

hydroxynaphthalene-4-sulfonic acid amide, Z-hydroxynaphthalene, 2--hydroxynaphthalene-4- or -6- or -7- or -8-sulfcnic acid, the corresponding sulfonic acid amides and methylsulfones, 1 amino 5-hydroxynaphthalene-7- sulfcnic acid, 2-amino-5-hydroxynaphthalene-7-sulfonic acid, 1 phenylamino 5 hydroxynaphthalene-7-sulfonic acid, 2 phenylamino 5 hydroxynaphthalene-7-sulfonic acid, 2 methylamino S hydroxynaphthalene-7-sulfonic acid, Z-ethylamino-S-hydroxynaphthalene-7-sulfonic acid, 2 4-bydro :y-3 -carboxy) -phenylamino-S hydroxynaphtharcne7-sulfonic acid, 2 -phenylamino-S-hydroxynaphthalene-7,4-disulfonic acid, 2 acetylamino S-hydroxynaphthalene-7-sulfonic acid, Z-benzoylamino-S-hydroxynaphthalene-7-sulfonic acid, 2 amino 8 hydroxynaphthalene-6-sulfonic acid, 2-benzoylamino-S-hydroxynaphthalene-d-sulfonic acid, 2-methylamino-S-hydroxynaphthalene-6-sulfonic acid, Z-hydroxyethylamino-8-hydroxynaphthalene 6 sulfonic acid, 1-arnino-8-hydroxynaphthalenet-sulfonic acid, 1-amino-8-hydroxynaphthalene- 2,4-disulfonic acid, 1- amino-8-hydroxynaphthalene-3,6- disulfonic acid and Z-butylamino-8-hydroxynaphthalene- 3,6-disulfonic acid.

In the production of symmetrical dyestuffs, the one mol of tetrazo compound of 4,4'-diamino-1',1'-diphenyl (II) is coupled sirnuitaneously with the two mols of azo compound (III). If unsymmetrical dyestuffs are being prepared, the tetrazo compound of (II) may be coupled either first with one mol of an azo compound (III) and then with one mol of an azo compound (III) different from the first-mentioned one, or the tetrazo compound is first coupled with one mol of compound (III) and then with any desired other azo component, it being possible in this connection to reverse the procedure and carry out the coupling first with the last-mentioned azo component. Valuable products can also be obtained with the simultaneous coupling of the te'trazo compound with a mixture of two difierent azo compounds (III). The first coupling generally takes place fairly rapidly and is advantageously carried out in a medium rendered alkaline with sodium carbonate. The resultant intermediate is either isolated or is further employed in solution without special working up. In order to accelerate the second coupling, it is desirable to add to the reaction solution an organic tertiary base, such as pyridine, quinoline or a technical pyridine base mixture. If the tetrazotized 4,4-diamino-1,l'-diphenyl is coupled simultaneously with both azo components, which may be the same or different from each other, the organic tertiary base which has an accelerating action is added to the coupling mass immediately at the beginning of the reaction.

The resulting polyazo dyestuffs are, if desired, salted out of the reaction solution. filtered and dried. The dyestuffs are readily soluble in water and may be employed for dyeing by the single bath or by the after-coppering process. A particularly valuble aftertreatment is that carried out with a salt of bivalent copper in the presence of a polymeric substance containing an imino or amino group, as for example those disclosed in U. S. Patent No. 2,622,075 of December 16, 1952.

The following examples set forth representative examplary embodiments of the invention. In these examples, the parts are by weight and the temperatures are in degrees centigrade.

Exampie 1 24.4 parts of 4,4'-diamino-3,3'-dimethoxy-l,1'-diphcnyl are tetrazotized. To the resultant tetrazo solution, there is added at 0-2 an alkaline solution of 51.5 parts of monoazo compound, obtained by the acid coupling of diazotized' 1 arnino-2-hydroxybenz-ene-5-sulfonic acid with 2 phenylamino 5 hydroxynaphthalene 7 sulfonic acid, and 10 parts of sodium carbonate in 1000 After the addition to the reaction mass on nois- NHCQHI sonar =N-Q- N=N- I on; on. H

dyestuff is precipitated, filtered and dried. It cor-responds and is a dark bronzy powder which dissolves with dark blue coloration in water and dyes cotton and fibers of HgCeOCHN- regenerated cellulose in navy blue shades. By treatment with copper sulfate by the oneor two-bath process, the dyeings are deepened and imparted a very good fastness to wet treatments.

By replacing the 2-phenylamino-5-hydroxynaphthalene- 7-sulfonic acid used in making the monoazo compound by 2-amino-5-hydroxynaphthaleneJ-sulfonic acid or by 2 methyl-amino-S-hydroxynaphthalene-7-sulfonic acid or by Z-hydroxyethylamino-5-hydroxynaphthalene-7-sulfonic acid or by 2-ethylamino-5-hydroxynaphthalene-7-sulfonic acid or by 2-propylamino-5-hydroXynaphthalene-7-sulfonic acid or by 2-cyclohexylamino-S-hydroxynaphthalene- 7-sulfonic acid or by 2-benzylaminO-S-hydroXynaphthalene-7-sulfonic acid or by 2-(3-carboxy-4-hydroxy)- phenylamino-S-hydroxynaphthalene-7-sulfonic acid, and otherwise proceeding as described in the preceding paragraph, there is in each case obtained a dyestuif with properties similar to those of the dyestutf obtained according to the said paragraph.

, Example 2 21.6 parts of 4,4'-diamino-3,3'dihydroxy-l,l'-dipl1enyl are tetrazotized. The isolated tetrazo compound is introduced into a solution of 34.3 parts of Z-benzoylamino- 6 8-hydroxynaphthalene-6-sulfonic acid, 10 parts of sodium carbonate and parts of pyridine in 600 parts of water and the resultant mass stirred for several hours at room temperature. The precipitated intermediate is isolated by filtration, introduced into a solution of 43.8 parts of the monoazo compound, obtained by the acid coupling of diazotized 1-amino-2-hydroxybenzene-S-sulfonic acid amide with 2-amino-S-hydroxynaphthalene-7-sulfonic acid, 4 parts of sodium hydroxide and 200 parts of pyridine in 1000 parts of water, after which the mass is stirred for several hours at 30. The formed trisazo to the formula H 0 8-- N Hz OzNH:

and is a dark powder which dissolves with blue coloration in water and dyes cotton and fibers of regenerated cellulose by the after-coppering process in blue shades which are characterized by noteworthy fastness to wet treatments and to light.

Dyestulfs with similar properties are obtained when, in the foregoing, the Z-benzoylamino-S-hydroxy-naphthalene- 6-sulfonic acid is replaced by the corresponding quantity of 1-hydroxynaphthalene-4-sulfonic acid or 2- hydroxynaphth'alene-4-sulfonic or 2-hydroxynaphthalene-6-sulfonic acid or 1-amino-8-hydroxynaphthalene-4-sulfonic acid or 1-amino-S-hydroxynaphthalene-7-sulfonic acid or 2-benzoylamino-5-hydroxynaphthalene-7-sulfonic acid.

Example 3 24.4 parts of 4.4'-diamino-3,3-dimethoxy-1,1'-diphenyl are tetrazotized and then coupled with 20.7 parts of lhydroxybenzene-Z-carboxylic acid in aqueous solution and in presence of sodium carbonate. After stirring for several hours, the formation of the intermediate is complete; the intermediate is then coupled in the presence of pyridine with 43.8 parts of the monoazo compound, obtained by the acid coupling of diazotized l-amino-Z-hydroxybenzene-S-sulfonic acid amide with 2-phenylamino- '7 S-hydroxynaphthalene-7-sulfonic acid, in aqueous solution. The trisazo dyestuir which is produced is precipitated, filteredand dried. It corresponds to the formula HOaS- HO O C CH3 0 0 H 0 H and is a dark bronzy powder which dissolves with a violet-black coloration in water and dyes cotton and fibers of regenerated cellulose in bluish black shades, which in the coppered state have noteworthy fastness properties. Dyestufis with similar properties are obtained when, in preparing the monoazo compound, referred to in the preceding paragraph, the 1-amino-2-hydroxybenzene-5-' sulfonic acid amide is replaced by l-amino-Z-hydroxybenzene-S-sulfonic acid or 1-amino-2-hydroxybenzene-5-sulionic acid-methylamide or 1-amino-2-hydroxybenzene-5- sulionic acid-phenylamide or 1-amino-2-hydroxy-4-nitrobenzene or 1-amino-Z-hydroxy-S-nitrobenzene or 1- amino-Z-hydroxy-S-chlorobenzene.

Example 4 244 parts of 4,4-diamino-3,3-dimethoxy-1,1'-diphenyl are tetrazotized. The tetrazo solution is then added, in the presence of pyridine, to an aqueous solution, rendered alkaline with sodium carbonate, of 95.2 parts of a mixture of monoazo compounds, which mixture is obtained by the acid coupling of one mol of diazotized 1-amino-2- hydroxybenzene-S-sulfonic acid amide with a mixture of 0.5 mol of Z-amino-5-hydroxynaphathalene 7 sulfonic acid and 0.5 mol of 2-phenylamino-5-hydroxynaphtha- HsCaHN- lene-7-sulfonic acid. The thus-obtained tetrakisazo dyestufi is salted out with sodium chloride, filtered and dried. It corresponds to the formula HOaS- HzNOzS HzH- 30:11

(5011; OCH:

and is a dark powder which dissolves with blue coloration in water and dyes cotton and fibers of regenerated cellulose in navy blue shades. The coppered dyeings possess outstanding fastness properties.

A whole series of additional tetrakisazo dyestuffs can be obtained according to the above-described mode of procedure, either by changing the proportions of 2- amino-S-hydroxynaphathalene-7-sulfonic acids used in preparing the monazo compound mixture or by replacing one or both components by one of the naphthalene compounds enumerated in Example 1 and diiferent from the naphthalene compounds mentioned in the preceding paragraph, or by replacing the diazotized l-amino-Z-hydroxybenzene-S-sulfonic acid amide by the diazo compound of one of the amines mentioned in Example 3, or finally by replacing the 4,4'-diamino-3,3'-dimethoxy-1,1'-diphenyl -NHC H ONE:

Example 5 24.4 parts of 4,4-diamino-3,3'-dimethoxy-1,l-diphenyl are tetrazotized. The tetrazo solution is combined, in the presence of sodium carbonate, with a solution of 47.3 parts of the monoazo compound, obtained by the acid coupling of the diazotized 1-amino-2-hydroxy-5-chlorobenzene-B-sulfonic acid with Z-amino-S-hydroxynaphthalene-7-sulfonic acid, in 1000 parts of water. Upon completion of the formation of the intermediate, there is added to the coupling mixture a solution of 40.3 parts of the monoazo compound, obtained by the acid coupling of diazotized Z-hydroxy-S-aminobenzene 1 carboxylic acid with Z-phenylamino-S hydroxynaphthalene 7 sul fonic acid, 10 parts of sodium carbonate, 200 parts of pyridine and 100 parts of water. The tetrakisazo dyestuff, which is thus formed and then isolated, corresponds to the formula and is a dark powder; it dissolves with blue coloration in water and dyes cotton and fibers of regenerated cellulose in blackish blue shades, which in the coppered state,

NHCoHs OaNHz possess noteworthy fastness properties.

Further examples are summarized in the following table. The coupling of the 4,4'-diamino-l,1-diphenyl with the two azo components is carried out according to the precedingly-described process. The first coupling is advantageously carried out in a medium rendered alkaline with sodium carbonate and the second may be carried out with the addition of for example pyridine, quinoline or a technical pyridine base mixture. The two couplings may be carried out simultaneously, in which event an organic tertiary base is advantageously added to the coupling mass at the very beginning in order to accelerate the reaction.

Example 8 OINHI HOaB- NHCOHB 010 Q H OOH 1, v H

Example 64 whereinX stands for a member selected from the group Consisting of OH, OCH;,, OC H OCH .COOH and parts of pre-wetted cotton are introduced into 300 OOOH, Y stands for a moiety corresponding to the parts of water at A concentrated aqueous solution containing 0.6 part of a dyestufi of any one of the fore- 4O formula going examples is then added to the bath, which is then heated, to boiling within 39 minutesf In the course of j the heating, there are added to the dye bath, in small HO:S NHR portions, 3 parts of sodium sulfate in the form of a concentrated aqueous solution. The bath is then maintained at boiling for an additional 30 minutes, 1 part of sqhumsuifate Ilsa/added then allowed 'R representing a member selected from the group con- 40 h dyed matenahsth-e? tlhoroughy sisting of monoand bi-nuclear aryl radicals of the rinsed and a ire-Sheba? conslstmg of 300 benzene series which are free from carboxylic acid parts of Water, P of acetic acld and P of groups and the OH substituent of which is in orthocopper sulfate, wherein it is treated for 30 minutes at position with respect to the adjacent N=N- group, 70?. 'I'heresu1tant'metallizeddyeing is rinsed and dried. Z Stands a member Selected from the group consisting The 0.3 part of copper sulfate of the aftertreatment of Foupling f P of the l i and naphthalel'le bath mentioned in the preceding paragraph may b6 series, wherein Y and Z may be 1dent1cal, and wherein R stands for va 'neniber selected from the group consisting Placed by partof a copper complex compound of of hydrogen, lower alkyl, lower hydroxyalkyl, monothe condensation product of diethylenetriamine and di- 2 g l 'a bq y vfiq qryh-cydqhexyl and cyandiamide (obtainable aecordmg to the process of U. S. v2 A. l i dyestfif'which corresponds to the Patent No. 2,622,-0 75 of Decernher l6, 1952) l for'mula f N=N--R'-0H -NHR ., V H Having thus disclosed the inventioniwha't is claimed wherein iv stands for avmember selected from the group 1. A polyazo dyestufl whieh-i =co. r,esponds to (the consisting of OCH and ,COOH, :1 stands for a member formula 3*, jg, 1i. M. selectedfrbm the. groupj consisting of hydrogen, NH

-NH.lower alkyl, -NH.cycloalkyl, -NH.aralkyl and z NH.aryl, b stands for a member selected from the group consisting of hydrogen and radicals of the formula X --N=N{-R'-}OH 15 n is one of the numerals 0 and 1, R stands for a. member selected from the group consisting of hydrogen, lower alkyl, lower hydroxyalkyl, mononuclear carbocyclic aryl,

cyclohexyl, and benzyl, and wherein R stands for a member selected from the group consisting of monoand binuclear aryl radicals of the benzene series which are free H|NO HgN-- S 01H 7 H CH: OH: H

7 V r V 30:11

CHgNOgB HsCeHN- 0 O H G O OH H References Cited in the file of this patent UNITED STATES PATENTS 16 from carboxylic acid groups and the OH substituent of which is in ortho-position with respect to the adjacent N=N group, the OH substituent in nucleus B being ,in ortho-position with respect to its adjacent N=N group.

3. The polyazo dyestuff corresponding to the formula OH Q nois- NHOIHI 0mm 4. The poly-azo dyestuff corresponding to the forrnula on. com

5. The polyazo dyestufi corresponding to the formula 6. The polyazo dyestufiz' corresponding to the formula 7. The polyazo dyestutf corresponding to the formula nmsr Nncu n Solon,

2,417,306 Krebser et al. Mar. 11, 1947 2,507,754 'Bossard et al. May 16, 1950 2,638,468 Wehrli May 12, 1953 2,644,812 Ruckstuhlet al. July 7, 1953 2,710,859 Kehrer et al. June 1-4, 1955 2,779,755 Ruckstuhl et al. Jan. 29, 1957 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2,842,538 July 8, 1958 Hans-Rudolf Byland It is herebf; certified that error appears in the-printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, lines 36 to 44, to the right of the formula appearing between those lines, at line 44, add III)-:-- as the number of the formula; column '7, lines 3'7 and 70, for "hydroxynaphathalene", each occurrence, read hydroxynaphthalene same column '7 in the formula of Example 4, left-hand portion, for "H H-" read H N Signed and sealed this 3rd day of March 1959.

(SEAL) Attest:

KARL AXLINE ROBERT c. WATSON Attesting Oflicer Commissioner of Patents 

1. A POLYAZO DYESTUFF WHICH CORRESPONDS TO THE FORMULA 